Methylene dioxyamine

ABSTRACT

A method for synthesizing the novel compound methylenedioxyamine through a reaction which involves the hydrolysis of methylene-O, O&#39;&#39;-bis (ethylacethydroximate).

Elmted States Patent 1 [111 3,714,199 McDowell et al. Jan. 30, 1973 [54]METHYLENE DIOXYAMINE [56] References Cited [75] inventors: Curtis S.McDowell, Edwards; UNITED STATES PATENTS Claude Merrill, Lancaster, bothof Calif 3,440,251 4/1969 Plllpovich ..260/350 3,383,417 5/]968Lichtenwalter ..260/584 R The United States of America as represented bythe Secretary of the Air Force Filed: March 17, 1970 Appl. No.: 24,945

Assignee:

US. Cl. ..260/350, 149/109, 260/583 DD Int. Cl ..C07c 83/00 Field ofSearch ..260/584 R, 584 C, 350

Primary ExaminerLeland A. Sebastian Att0rneyHarry A. Herbert, Jr. andWilliam J. O- Brien [57] ABSTRACT 2 Claims, No Drawings METHYLENEDIOXYAMINE BACKGROUND OF THE INVENTION This invention relates to a newcompound and to a method for its preparation. More particularly, thisinvention concerns itself with the synthesis of methylenedioxyamine andto a process for effecting that synthesis. Methylenedioxyamine, thenovel compound of this invention, is a useful intermediate or precursorin the formation of methylenedioxyamine diperchlorate. The diperchloratesalt is formed by a hydrolytic reaction between methylenedioxyamine andperchloric acid. The compound of this invention also finds utility as afuel or monopropellant in rocket propulsion systems.

SUMMARY OF THE INVENTION In the present invention, the synthesis ofmethylenedioxyamine is accomplished by reacting a solvent mixture ofmethylene- -bis (ethylacethydroximate) and 10 percent excessconcentrated hydrochloric acid.

The reaction is continued at a temperature and for a period of timesufficient to hydrolyze the methylene- 0,0'-bis (ethylacethydroximate).Generally, reaction times of from about 15 minutes to 24 hours attemperatures ranging from to 100 C have been found suitable. A solventsuch as ether, glyme, diglyme, nitromethane, or other suitable solventsof similar polarity may be used as the solvent component. The resultanthydrolytic reaction product is methylenedioxyamine dihydrochloridewhich, in turn, is neutralized with a suitable base such as sodium orpotassium hydroxide in a suitable solvent such as methanol or ethanol.This gives methylenedioxyamine upon filtration and distillation of thesolvent phase.

Accordingly, the primary object of this invention is to provide a newcompound and a method for its preparation.

Another object of this invention is to provide a method for thesynthesis of methylenedioxyamine.

The above and still other objects and advantages of this invention willbecome readily apparent upon consideration of the following detaileddescription thereof.

DESCRIPTION OF THE PREFERRED EMBODIMENT In accordance with thisinvention, it has been found that the above-noted objects can beaccomplished by a reaction in which methylene-0,0'-bis(ethylacethydroximate) is hydrolyzed using percent excess concentratedhydrochloric acid in either glyme or some other suitable solvent ofsimilar polarity. The resultant produce is methylenedioxyaminedihydrochloride which, in turn, is neutralized in a solvent mixture ofeither sodium or potassium hydroxide to give methylene dioxyamine afterfiltration and distillation of the solvent phase.

The reaction which is believed to take place during the synthesis of thenovel compound of this invention is illustrated by the followingschematic representation:

[OH3C(OEt)NOIjCHI H01 (aqueous) (solvent) CHAONHaCl): 01130 OgEtsynthesis of methylenedioxyamine according to the process of theinvention, a quantity of a solvent such as diglyme, glyme, ether,nitromethane or other solvent of similar polarity is added tomethylene-0,0'-bis (ethylacethydroximate). Concentrated hydrochloricacid is then added to the mixture, 10 percent in excess ofstoichiometry, and the mixture is stirred preferably at a temperature ofapproximately 40-50 C for about 15 minutes to 2 hours. The resultantwhite solid is filtered from the reaction mixture, washed with asuitable solvent, such as ether, and dried in air. The white solidmethylenedioxyamine dihydrochloride is then taken up in ethanol(methanol or other solvents of appropriate polarity may be used) andtreated with a stoichiometric quantity of base, such as potassiumhydroxide or sodium hydroxide. The resultant mixture is filtered, dried,and the filtrate distilled to partially remove the solvent. Theremaining solvent-dioxyamine mixture is then vacuum distilled to yieldthe free methylenedioxyamine.

In order to further illustrate to those skilled in the art the best modeof operation for the present invention, there is presented the followingdetailed example. This example, however, is presented for purposes ofillustration only and is not to be considered as limiting the scope ofthe invention in any way.-

EXAMPLE -To 100 ml of dry diglyme was added 10.0g (0.046 mole) ofmethylene-0,0-bis (ethylacethydroximate) and 8.4 ml (10 percent excess)of concentrated hydrochloric acid. The mixture was stirred at 50 C for15 minutes, filtered and the solid washed with two 50 ml portions ofether. The resultant solid passed a melting point of l54155 C and, whendried, weighed 6.5g (94 percent).

Analysis calculated for C H Cl N O C, 7.95; H, 5.34; N, 18.54: CI, 47.0:Analysis found to be: C, 8.1; H, 5.3; N, 18.5; C1 46.1. Infraredabsorption spectra was found to be compatible with the assignedstructure for To cc of methyl alcohol was added 3.30g of 98 percentsodium hydroxide (0.0825 mole). After the sodium hydroxide dissolved,6.07g (0.0402 mole) of the methylenedioxyamine dihydrochloride preparedabove was added and the mixture stirred for 1 hour. The resultantprecipitate was filtered and washed with methyl alcohol. The filtratewas dried over anhydrous calcium sulfate and refiltered. The methylalcohol was evaporated on a rotary evaporator under reduced pres-- sureat 3050 C. The resultant oil was distilled in a molecular still to give2.34g percent) of a colorless oil, methylenedioxyamine with a meltingpoint of 8 to 9 C and a boiling point of 67 C at 3 mm. Infraredabsorption and nuclear magnetic resonance spectra were compatible withthe assigned structure.

mixture of methylene-0,0'-bis (ethylacethydroximate) and hydrochloricacid, (2) filtering said hydrolytic reaction product, (3) neutralizing asolvent mixture of said filtered reaction product and (4) separatingsaid neutralized filtrate from said solvent by distillation.

solvent

1. The compound, methylenedioxyamine.